Sizing of yarns and fibers with combinations of polymers and crosslinking agents

ABSTRACT

THIS INVENTION RELATES TO A PROCESS FOR PRODUCING A DURABLE-PRESS FABRIC HAVING A SUPERIOR ABRASION RESISTANCE. CELLULOSIC TEXTILE YARNS ARE SIZED WITH A COMBINATION OF A PERMANENT POLYMER, A TEMPORARY POLYMER AND A CROSSLINKING AGENT PRIOR TO WEAVING. THE PERMANENT POLYMER INCLUDES POLYURETHANES, POLYACRYLATES, BUTADIENE-STYRENE COPOLYMERS, BUTADIENE-ACRYLONITRILE COPOLYMERS, AND ETHYLENE-VINYLACETATE COPOLYMERS. A TEMPORARY POLYMER IS POLYVINYL ALCOHOL. CROSSLINKING AGENTS INCLUDE DIMETHYLOL DIHYDROXY-ETHYLENUREA (DMDHEU), DIMETHYLOL METHOXYETHYLACARBAMATE, METHYLOL MELAMINE, AND DIMETHYLOL PROPYLENEUREA.

United States Patent Ofice 3,666,400 Patented May 30, 1972 SIZING OFYARNS AND FIBERS WITH COMBINA- TIONS OF POLYMERS AND CROSSLINKING AGENTSJohn T. Lofton and Robert J. Harper, In, Metairie, and Eugene J.Blanchard, New Orleans, La., assignors to the United States of Americaas represented by the Secretary of Agriculture No Drawing.Continuation-impart of application Ser. No. 756,323, Aug. 29, 1968. Thisapplication Mar. 10, 1970, Ser. No. 18,292

Int. Cl. D06m 13/52, 15/70 US. Cl. 8115.6 Claims ABSTRACT OF THEDISCLOSURE This invention relates to a process for producing adurable-press fabric having a superior abrasion resistance. Cellulosictextile yarns are sized with a combination of a permanent polymer, atemporary polymer and a crosslinking agent prior to weaving. Thepermanent polymer includes polyurethanes, polyacrylates,butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, andethylene-vinylacetate copolymers. A temporary polymer is polyvinylalcohol. Crosslinking agents include dimethylol dihydroxy-ethylenurea(DMDHEU), dimethylol methoX- yethylcarbamate, methylol melamine, anddimethylol propyleneurea.

This is a continuation-in-part of Ser. No. 756,323 filed Aug. 29', 1968,now abandoned.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

The primary object of this invention is to provide a method forproducing durable-press fabrics with superior abrasion resistance. Inthis method, textile fibers and crosslinking agents are sized with acombination of permanent polymer additive, temporary polymer agent andcrosslinking agent prior to weaving. The polymer additive employed isone which improves the wrinkle recovery or abrasion resistance whenapplied to woven fabric. By application of the polymer additive to theyarn, prior to weaving, the polymer additive serves the dual purpose ofacting as a weaving size and improving the wrinkle recovery of thefinished fabric. The use of a crosslinking agent in conjunction with thetemporary sizing agent provides a method by which the temporary agentbecomes permanently attached to the fabric. By use of the crosslinkingagent in the size, a less than normal amount of crosslinking agent canbe utilized in finishing the fabric subsequent to weaving. Thisprocedure provides a method of producing fabrics with smooth dryingappearance and improved abrasion resistance.

Heretofore sizing mixtures have been designed to be temporary and areremoved by desizing operations immediately after weaving. Permanentpolymers are then applied to the fabric. Polymers applied to the fabrictend to stiffen the fabric and at times lead to undesirable yarnbinding. This higher degree of stiffness is detrimental from theviewpoint of the esthetics of the fabric to the wearer as well asabrasion resistance in the garment manufactured from such fabrics.

By the process of this invention, polymers and crosslinking agents canbe applied to yarns in the normal manner that starch size is applied.The types of polymers which have been successfully utilized have beenpolyurethanes, polyacrylates, and butadiene-styrene copolymers. Thetypes of temporary sizing agents used in this research include polyvinylalcohol and carboxymethyl cellulose. The types of crosslinking agentsused include dimethylol dihydroxyethyleneurea and methylol melamines.The warp yarn is passed through the emulsion, squeezed, and dried andcured in some cases. The resulting warp beam is then loomed and woveninto a fabric. The woven fabric can be scoured, bleached, and dyed.Durable-press crosslinking agents and other finishing auxiliaries arethen padded onto the fabric and dried.

The advantages of using permanent polymer sizing are many. Polymers canbe applied to the yarns in the normal manner that starch size is appliedat the slasher. This. eliminates the desizing procedure normallyencountered in the application of a temporary sizing. Efficiency inweaving is equal to or better than regular starch size. It is alsopossible to vary the conditions of sizing. For example, you can usepermanent sizing in warp and filling, permanent sizing in the warpdirection only, or a combination of permanent and temporary sizing.Another advantage of applying the permanent polymer to the yarn and thenweaving the fabric in contrast to application of the polymer to thewoven fabric is that the resultant yarn treated fabrics are softer thanthe fabrics treated with the same polymer add-on. This reduced stifinessimproves edge abrasion resistance. Durable-press fabrics, which havepolymers only in the warp direction, do not have the exceedingly lowcrease sharpness values exhibited by fabrics which have been treatedwith the same polymers as fabric treatments.

Yarns can be sized with a combination of temporary and permanent sizingagents. This type formulation has cost advantages over the use ofpermanent sizing agents only. Under certain conditions temporary agentssuch as PVA/CMC can be crosslinked to produce fabrics with excellentdurable-press performances and a substantial improvement in fabricstrength properties.

In this method, textile fibers/yarns are sized with permanent polymersand combinations of these ingredients with crosslinking resins. Thismethod produces good durable-press fabrics with low resinconcentrations; thus improving physical properties with cost savingfinishes. Directional application of polymer and crosslinking agents canbe used to control physical properties, wrinkle recovery, and abrasionresistance of a preferred yarn direction in the finished fabric.

Other variations to this same basic treatment are also possible. A briefdescription and explanation of these variations will be given.

First, it is possible to prepare fabrics from polymer sized warp andfilling yarns, and it is also possible to prepare fabrics from yarnstreated with a combination of polymers and crosslinking agents. If thesame polymer and crosslinking agent are used for both the warp andfilling treatment, the resultant fabric is softer than the fabrictreated with the same polymer. The yarn-treated fabrics then can beraised to durable-press performance with a lower level of crosslinkingtreatment or an equivalent level of crosslinking treatment. Theyarn-treated fabric is softer and has improved abrasion resistance.

In a second variation, yarns were sized with one polymer in the warpdirection and a second polymer in the filling direction. No such fabriccan be produced from a fabric treatment and the types of polymers usedfor the warp and filling treatments can be used to control or modifyfinal properties such as breaking strength, crease sharpness, fabricstiffness and other properties.

A special variation of sized warp and filling yarn fabrics can beemployed to achieve certain unique fabric properties. Thus, it was foundthat heavyweight fabrics prepared from warp and filling polymer-treatedyarns (particularly 2-ply yarns) can be used to produce a fabric whichhas good wash-wear appearance with no further treatment other thanapplication of a softener. Cuffs prepared from such fabrics showed goodwash-wear appearance and crease sharpness through 30 launderings. The

4 The following examples illustrate but do not limit the scope of thisinvention. All percentages are by weight.

EXAMPLE 1 1% of a zinc nitrate based solution. Loom run.

smooth drying and crease sharpness of such fabrics arise An twill fabricwas woven from Warp and fining from the heat-set treatment of thepolymer. Such fabrics, yams sized with 2% PVA and 2 7% lowmmperamretherefore, have the special advantage of no odor release in DMDHEU and1% of a zinc I'fitrate base catalyst the cutting room. A secondadvantage would be that the Warp yams were cumd on Slasher dry cans; fasia:instantiate?asserts; g t a ment with these heavyweight goods is thatthe warp and ig gi 22 g ig gs gfi? d 2 gigigggf ggg g gg m fgg g ggz g g$23: 1.4% of a zinc nitrate base catalyst. The second salmpql e intotrousers and then heat set to produce crease and 2?; if i giggg gig gSfi zg g ggg 123 6: as: 32 3213223.?i5223i,1223.333.i ttif fififfii? g ofdehyde odor in garment plants) with the further ad- S$2 fiz ggi i i igfigggg fg g; gf g gi zz iifi i fi ggigi g ggggr appearance andennitrate based catalyst. All three fabrics had comparable Anothergeneral area of variation in these yarn-treated g a gg i 2?? the 1st and20th Wash fabrics would be to use a combination of permanent and eye Sare 5 Wm m a e temporary (standard) size in these yarn treatments. TheEXAMPLE 2 temporary size may then be removed leaving the desired levelof permanent size. This approach has the advantage In another experimentthe above fabric was woven of economy since the polymers used inpermanent sizing from warp yarns treated with 2.5% solids polyurethane,generally are more expensive than temporary size agents. 3% PVA, 2.7%solution DMDHEU and 1% of a zinc A further variation of the use ofpermanent and temporary nitrate based catalyst, and an untreatedfilling. One porsizing was observed when such fabric Was crosslinkcdtion of the fabric was desized, scoured, and treated with without anyintermediate desizing operation. In several a 4% solution of DMDHEU. Theother portion was cases where both the warp and filling yarns were testecured on a tenter frame at 320 F., desized, scoured, and withcombinations of permanent and temporary sizes and treated with a 1.8%solution DMDHEU and 0.5% of a crosslinked Without desizing, fabrics wereobtained with zinc nitrate base catalyst. Results in Table II. 300 WRAand exceedingly high retention of breaking strength. For example,breaking strength retention was XA 3 96% in the warp direction and 85%in the filling direcp tion. By contrast a conventional treatment on thenon- In another extferlment, a fabric Was woven from p polymer-treated(control) fabric had 39% retention in Y treated with 4 {nethylolmelamlfle d 3% the warp direction and 32% retention in the fillingdirec- PVA and 0.5% of a 11116 filtrate base catalysi- A Partlal tioncure was dgne ondtiheistealrlnfar; as:4 513113 gagric avalsqther 40scoured an repa e wi 0 an 0 o ggg a g fg g ggz 2122113238 3 322233335333 a zirrdc nitrate base catalyst. The fabric was then dried andtem orar size and crosslinkin a ents in the yarn treatcure y men is.Tiivo variables are pos sibli in this case. In one fi Second, fabnc wassimilarly i fixcept the w variation, a partial cure is applied to yarnsso that only a z ig POPaCFYIate addmon to 3% a part of temporary size isremoved in the desizing operaan 0 me y 0 me l tion. In the second case,a full cure is applied to yarns A was also i m Winch the crosslinkmgagent prior to desizing. By this latter method, most of the was apphed qz and scoured fabnc only The temporary size is converted to a permanentpolymer additr.eatm.em conslste 0 63% DMD HEU and 25% of a five on thefabric zinc nitrate base catalyst.

Results are shown in Table III. Permanent polymers which can be used bythe process of this invention include polyurethanes, polyacrylates,EXAMPLE 4 butadiene-styrene copolymeri, butadiene-acrylonitrile co-Polymers, and etbylene'vinylacetbte PP in the In another experiment, thefabric was woven from warp Tange 0f ab11t4% to 20% y Welghtwith filllngYarns, yarn treated with 8% polyacrylate, 3% PVA, 1.4% Polymers can beused in the range from 1% W 20% and DMDHEU and 0.5% of a zinc nitratebase catalyst. The can a so include Silicones, Polyethylene and P YP PYfilling yarns were untreated. After the fabric was woven, cfosslinkingagents inclbde dimethylol dihydroxy' it was given a full cure. Thefabric was then scoured and ethyleneurea dimethylolmethoxyethylcarpadded with 3.6% DMDHEU and 1.5% of a zinc nitratebamate, and methylol melamine propyleneurea in the b catalyst Th fabriwas h d i d range of about 1% to 20% y Weight and p rary A desized,scoured and bleached control twill fabric polymers include polyvinylalcohol (PVA), carboxywas padded with 8.1% DMDHEU and 3% of a zincmethyl cellulose (CMC), and starch in the range of about nitrate basecatalyst. The fabric was dried and. cured in 1% to 15% by weight. theusual fashion. Results are shown in Table IV.

TABLE I Flo; Grab Tear Wash- Washsample abrasion strength strength wees,wzeflntrii Creaggi Cre2a)s"eh, No. Treatment Warp Fill Warp Fill WarpFill wash wash wash Wash 507 Control-6.3% sol. DMDHEU plus 2.5% of azinc 57 118 49.7 54.7 1,367 1,433 5 4.9 5 4.9

nitrate based solution. Desized-scoured. 505 Warp and fil1ing2% PVA plus2.7% DMDHEU 178 467 62.5 66.5 1,650 1,700 4.7 4.7 4.8 4.6

(and 1% of zinc nitrate based solution) fabric- 3.6% DMDHEU and 1.5% ofa zinc nitrate based solution. Desized-seoured. 509 Warp and nu2% PVAplus 2.7% DMDHEU and 777 1,275 90.5 81 2,283 2.117 4.2 4.1 4.9 4.9

TABLE II Flex Grab Tear Wash- Washabrasion strength strength wear, wear,Crease, Crease, Sample 20th 1st 20th No. Treatment Warp Fill Warp Fillwarp Fill wash wash Wash waslr 5C7 ControlDesized-scoured, 6.3% DMDHEUand 57 118 49.7 54.7 1,367 1,433 5 4.9 5 4.9

2.5% zinc nitrate based catalyst. 7-P-14. Warp-2.5% polyurethane, 3%PVA2.7 sol. 332 886 68.4 54.7 1,733 1,533 4.5 4.7 4.9 4.7

DMDHEU and 1% of zinc nitrate based catalyst, glelsized-scoured 1.8%sol. DMDHEU untreated 7P2-4. Cured320 F.,desized-scoured,1.8% sol.DMDHEU 990 2,058 88. 2 63.2 2, 533 1,633 4.2 3. 5 4.4 4.3

and 0.5% zinc nitrate based catalyst.

TABLE III [2 x 1 twill, 8.5 z./sq. yd.]

Flex Grab Tear abrasion Strength Strength Sample No. Treatment WarpFilling Warp Filling Warp Filling CRA C7 ControlE6.3% sol. DMDHEU plus2.5% zinc nitrate solution. Desized- 57 118 49.7 54.7 1,367 1,433 270scoure 8P1-6 Secured-2.7% sol. DMDHEU plus 1% of zinc nitrate basedsolution. 1 3,008 3,337 106 1 84 1 3,000 2, 227 243 Warp-3% PVA, 2.4%methylol melamine. Filling untreated. 9P1-6 Scoured2.7% sol. DMDHEU plus1% zinc nitrate based solution. Warp 1, 473 1, 555 92 70 2, 633 2, 000255 8% polyacrylate, 3% PVA, 2.4% methylol melamine. Filling untreated.

1 Partial cure on cans.

TABLE IV [2 x 2 twill, 8.5 oz./sq. yd.]

Grab strength Sample Wash- No. Treatment Warp Filling ORA wear Crease4C8 Control-Desized, scoured,bleaehed. 8.1% sol. DMDHEU and 3% of a 6553 281 4.7 5.0

zine nitrate based catalyst. 1518 Warp8% polyacrylate, 3% PVA, 1.4% sol.DMDHEU and 0.5% of a 1 87 1 68 1 232 1 4 1 5 zinc nitrate basedcatalyst. Filling-untreated. Fabricscoured3.6%

DMDHEU and 1.5% of a zinc nitrate based catalyst.

1 Full cure before scouring.

We claim:

1. A process for producing a durable-press fabric with superior abrasionresistance comprising:

(a) treating cellulosic textile warp and filling yarns with an emulsionconsisting of about from 4% to 20% by weight of a permanent polymerselected from the group consisting of polyurethanes, polyacrylates,butadiene-styrene copolymers, butadieneacrylonitrile copolymers, andethylene-vinylacetate copolymers, about from 1% to 20% by weight of acrosslinking agent selected from the group consisting of dimethyloldihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylolpropyleneurea, and methylol melamine, and about from 0.5 to 1.5% byweight of a base catalyst, and drying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured yarns of steps(a); and

(c) crosslinking the woven fabric from step (b) with about from 1% to20% by weight of a crosslinking agent selected from the group consistingof methylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate,dimethylol propyleneurea, and methylol melamine.

2. A process for producing a durable-press fabric with superior abrasionresistance comprising:

(a) treating cellulosic textile warp and filling yarns with an emulsionconsisting of about from 1% to by weight of polyvinyl alcohol, aboutfrom 1% to by weight of a crosslinking agent selected from the groupconsisting of dimethylol dihydroxyethyleneurea, dimethylolmethoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine,and about from 0.5% to 1.5% by weight of zinc nitrate base catalyst, anddrying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured yarns of step(a); and

(c) crosslinking the woven fabric from step (b) with about from 1% to 2%by weight of a crosslinking agent selected from the group consisting ofdimethylol dihydroxyethyleneurea, dimethylol met-hoxyethylcarbamate,dimethylol propyleneurea, and methylol melamine.

3. A process for producing a durable-press fabric with superior abrasionresistance comprising:

(a) treating cellulosic textile warp yarns with an emulsion consistingof about from 4% to 20% by weight of a permanent polymer selected fromthe group consisting of polyurethanes, polyacrylates, butadienestyrenecopolymers, butadiene-acrylonitrile copolymers, and ethylene vinylacetate copolymers, about from 1% to 15% by weight of polyvinyl alcohol,about from 1% to 20% by weight of a crosslinking agent selected from thegroup consisting of dimethylol dihydroxyethyleneurea, dimethylolmethoxyethylcarbamate, dimethylol propyleneurea, and methylol melamine,and about from 0.5% to 1.5 by weight of zinc nitrate base catalyst, anddrying and curing the thus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured warp yarns ofstep (a) and untreated filling yarns; and

(c) crosslinking the woven fabric from step (b) with about from 1% to20% by weight of a crosslinking agent selected from the group consistingof dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate,dimethylol propyleneurea, and methylol melamine.

4. A process for producing a durable-press fabric with superior abrasionresistance comprising:

(a) treating cellulosic textile warp yarns with an emulsion consistingof about from 4% to 20% by weight of a permanent polymer selected fromthe group consisting of polyurethanes, polyacrylates, butadienestyrenecopolymers, butadiene-acrylonitrile copolymers, and ethylene-vinylacetate copolymers, about from 1% to 20% by weight of a crosslinkingagent selected from the group consisting of dimethyloldihydroxyethyleneurea, dimethylol methoxyethylcarbamate, dimethylolpropyleneurea, and methylol melamine, and about from 0.5% to 1.5% byweight of zinc nitrate base catalyst, and drying and curing thethus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured warp yarns ofstep (a) and untreated filling yarns; and

(c) crosslinking the woven fabric from step (b) with about from 1% to20% by weight of a crosslinking agent selected from the group consistingof dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate,dimethylol propyleneurea and methylol melamine.

5. A process for producing a durable-press fabric with superior abrasionresistance comprising:

(a) treating cellulosic textile warp yarns with an emulsion consistingof about from 1% to 15% by polyvinyl alcohol, about from 1% to 20% byweight of a crosslinking agent selected from the group consisting ofdimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate,dimethylol propyleneurea, and methylol melamine, and about from 0.5% to1.5% by weight of a base catalyst, and drying and curing thethus-treated yarns;

(b) weaving a fabric from the treated, dried, and cured warp yarns ofstep (a) and untreated filling yarns; and

(c) crosslinking the Woven fabric from step (b) with about from 1% to20% by weight of a crosslinking agent selected from the group consistingof dimethylol dihydroxyethyleneurea, dimethylol methoxyethylcarbamate,dimethylol propyleneurea, and methylol melamine.

References Cited WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS,Assistant Examiner US. Cl. X.R.

8-1163; 117-1394, 139.5 A, 143 A 161 KP, UD, UC, UE

